EP0348532A1

EP0348532A1 - Process for processing silver halide photographic material

Info

Publication number: EP0348532A1
Application number: EP89901302A
Authority: EP
Inventors: Shinji Ueda; Tetsuro Kojima; Tohru Kitahara; Tomokazu Yasuda; Yoshihiro Fujita; Takatoshi Ishikawa
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1988-01-06
Filing date: 1989-01-06
Publication date: 1990-01-03
Anticipated expiration: 2009-01-06
Also published as: US5194368A; EP0348532B1; EP0348532A4; WO1989006381A1; DE68919761D1; DE68919761T2

Abstract

A process for processing a silver halide photographic material having a silver halide emulsion layer comprising at least one silver iodide layer with a processing solution which can develop and fix the photographic material, which comprises conducting said processing while bringing the processing solution into contact with an anion exchange resin in an amount of 20 to 2000 i of said processing solution per liter of said anion exchange resin. This process is intended to accelerate fixing and reduce the amount of waste fixing solution.

Description

TECHNICAL FIELD

The present invention relates to a method for processing silver halide photographic light-sensitive materials having silver halide emulsion layer containing silver iodobromide and more specifically to a method for processing such photographic light-sensitive materials, which comprises a desilvering capable of rapidly fixing the light-sensitive materials and capable of reducing the amount of waste of a processing solution having fixing ability.

BACKGROUND TECHNIQUES

Basic processes for processing silver halide light-sensitive materials, for instance, color light-sensitive materials are a color developing process and a desilvering process. In the color developing process, the silver halide exposed to light is reduced with a color developing agent to form elemental silver and simultaneously the oxidized color developing agent reacts with a coupler to form dye images. In the subsequent desilvering process, the elemental silver formed during the color developing process is oxidized by the action of an oxidizing agent (in general, referred to as "bleaching agent ") and then is dissolved by the action of a complexing agent generally referred to as "fixing agent". Only the dye images remain on the color light-sensitive materials through such a desilvering process.
The desilvering process described above generally comprises two processing baths, one of which is a bleaching bath containing a bleaching agent and the other of which is a fixing bath containing a fixing agent; or one bath, i.e., a bleach-fixing bath simultaneously containing a bleaching agent and a fixing agent.
The practical development processing futher comprises, in addition to the foregoing basic processes, a variety of auxiliary processes for the purpose of maintaining photographic and physical properties of images, enhancing storability of images or the like. Examples of such auxiliary processes or baths are a film hardening bath, a stopping bath, an image stabilizing bath and a water washing bath.
If a light-sensitive material composed of an emulsion containing silver iodide such as a color negative light-sensitive material for taking photographs is desilvered, it takes a long period of time and, therefore, there is a strong demand to develop a method in which the time required for desilvering can substantially be shortened.
It is also required to reduce the amount of waste liquor derived from photographic processing from the viewpoint of preventing environmental pollution and in the desilvering process, it becomes an important subject to reduce the amount of waste liquor, for instance, by reducing the amount of a fixing solution to be replenished.
Incidentally, there have been conducted various studies to develop a means for recovering silver as a valuable noble metal from bleach-fixing or fixing solutions, for instance, a method for recovering silver by introducing a bleach-fixing solution in an electrolytic cell and then electrolyzing it; a method for recovering silver by diluting the bleach-fixing solution to lower the solubility of a silver salt to precipitate the same; a method for recovering silver by adding sodium sulfide to these solutions in order to form silver sulfide; or a method for recovering silver, in the form of ions, by passing such a solution through a column packed with a large amount of an ion-exchange resin. Such means for recovering silver are detailed in, for instance, Kodak Publication, J-10 (Recovering Silver From Photographic Material), issued by Kodak Industrial Division; J.P. KOKOKU No. 58-22528; J.P. KOKAI No. 54-19496; Belgian Patent No. 869,087; and DEOS No. 2,630,661.
However, these methods are developed to recover silver from bleach-fixing solutions, but not to reuse the solutions obtained after the recovery of silver. Therefore, there are various obstacles to reuse such bleach-fixing solutions after desilvering. For instance, the bleach-fixing solutions obtained after the desilvering cannot be reused or it is necessary to add components which are lost during the recovering of silver (addition of a regenerant) to reuse the same. As described above, it has not yet been realized to simultaneously reduce the amount of waste liquor and rapidly carry out the desilvering process while recovering silver.
Accordingly, an object of the present invention is to provide a method for processing silver halide photographic light-sensitive materials, which makes it possible to carry out a rapid fixing process compared with conventional methods and to reduce the amount of waste liquor of a processing solution having fixing ability.

DESCLOSURE OF THE INVENTION

The present invention relates to a method which comprises processing, with a processing solution having fixing ability, a silver halide photographic light-sensitive material composed of a substrate provided thereon with at least one silver halide emulsion layer containing silver iodide after developing it and which is characterized in that the processing with the processing solution having fixing ability is carried out while a part or whole thereof is brought into contact with an anion-exchange resin and that the amount of the processing solution having fixing ability to be brought into contact with the resin is adjusted to 20 to 2000 liters per liter of the anion-exchange resin.
In the method of this invention, the processing of the light-sensitive materials can continuously be performed by exchanging the used anion-exchange resin with new one at the time when the amount of the processing solution reaches 2000 liters or before it reaches the upper limit.
The inventors of this invention have conducted various studies and have found that a processing solution having fixing ability (hereunder sometimes referred to as "fixing processing solution") deteriorated through the processing of photographic light-sensitive materials containing silver iodide comprises a large amount of silver ions and a small amount of iodide ions and that the fixing ability thereof is extremely lowered by the action of both these ions. However. if silver ions present in the deteriorated processing solution having fixing ability is recovered by any means for recovering silver as described above, the thiosulfate serving as a fixing agent or sulfite ions serving as a preservative thereof are decomposed or removed during the recovery of silver.
Contrary to this, the inventors of this invention have found that the fixing ability of, the processing solution having fixing ability can be sufficiently recovered by removing iodide ions, although silver ions are still present therein and that the iodide ions among inorganic ions present in the solution can almost selectively be removed from the deteriorated processing solution by bringing it into contact with an anion-exchange resin. It is also found that there is a certain optimum range with respect to the cumulative amount of the processing solution having fixing ability to be in contact with anion-exchange resin per unit volume of the anion-exchange resin.
Moreover, if the time required for a processing with a bath having fixing ability and the subsequent water washing and/or stabilization processes is shortened (for instance, not more than 5 min.), it is liable to cause a problem of increasing magenta stain (Dmin) during continuous processing. However, if the processing is performed using an anion-exchange resin as in the present invention, such a problem does not arise. Therefore, the method is quite favorable for rapid processings. It is assumed that this is resulted from the removal of colored contaminants such as dyes by means of the anion-exchange resin.
In the method of this invention, 20 to 2000£ of a fixing processing solution per liter of an anion-exchange resin is brought into contact with the resin. More specifically, if more than 2000 l of the fixing processing solution is treated with one liter of the resin, iodide ions present therein are not sufficiently removed with the resin, while if less than 202 of the fixing processing solution is treated with one liter of the resin, the amount of thiosulfate serving as a fixing agent removed by the resin in addition to iodide ions increases, which results in the necessity of supplementing a thiosulfate as a regenerant to the processing solution. In the latter case, the amount of the resin used increases and thus it is not preferred from the economical viewpoint. In addition, if silver ions are removed from the processing solution having fixing ability utilizing an ion-exchange resin, they are conventionally removed in the form of thiosulfate salts with the resin and, therefore, the fixing processing solution treated with the resin amounts to the order of 5 to 152 per liter of the resin.
The light-sensitive materials which are processed by the method of the present invention comprise a silver halide emulsion layer. The light-sensitive material preferably comprises at least one silver halide emulsion layer containing at least one mole% of silver iodide, preferably 5 to 25 mole% and more preferably 7 to 20 mole%.
Therefore, the color light-sensitive material is formed by applying onto a substrate, at least one layer of silver halide emulsion which contains at least one silver iodide selected from the group consisting of silver iodide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. In this respect, silver chloride and silver bromide may optionally be used in addition to the foregoing silver iodide.
The silver halide grains used in the color photographic light-sensitive materials of the present invention may be in the form of any crystalline forms such a regular crystalline form as a cubic, octahedral, rhombododecahedral or tetradecahedral form; such an irregular form as a spheric or tabular form; or a composite form thereof. In addition, they may be tabular grains having an aspect ratio of not less than 5 as disclosed in Research Disclosure, Vol. 225. pp. 20 - 58 (January, 1983). The silver halide grains may be those having epitaxial structure or those having a multilayered structure whose internal composition (such as halogen composition) differs from that of the surface region.
The average grain size of the silver halide is preferably not less than 0.5 µ , more preferably not less than 0.7 and not more than S.Oµ .
The grain size distribution thereof may be either wide or narrow. The latter is known as so-called monodisperse emulsions whose dispersion coefficient is preferably not more than 20% and more preferably not more than 15%. The "dispersion coefficient" herein means the standard deviation divided by the average gain size.
The coated amount of silver in the light-sensitive materials of the present invention is generally 1 to 20 g/ m², preferably 2 to 10 g/ m² , provided that the total amount of iodine (AgI) present in the silver halide light-sensitive materials is preferably not less than 4 x 10^-3 mole/ m² and more preferably not less than 6 x 10-³ mole/ m² and not more than 4 x 10-² mole/m² .
The silver halide emulsions may contain other salts or complexes such as cadmium salts, zinz salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof and iron salts or complex salts thereof, which are added thereto during the formation of silver halide grains or physical ripening process.
The term "processing solutions having fixing ability" herein means a bleach-fixing solution or a fixing solution.
If the processing solution having fixing ability is a bleach-fixing solution, a bleaching accelerator may be used.
According to the method of this invention, iodide ions can be removed. As a result, the amount of the fixing processing solution replenished can be reduced and simultaneously the amount of waste liquor can be reduced. Therefore, the present invention is to provide a rapid processing method which can not cost and has low probability of causing environmental pollution.
Various commercially available resins may be used as the anion-exchange resins as used herein. In particular, in the present invention, basic anion-exchange resins are preferably used as such anion-exchange resin.
Preferred basic anion-exchange resins used in the invention are represented by the formula (VIII):
In the formula, A represents a monomer unit obtained by copolymerizing copolymerizable monomers having at least two ethylenically unsaturated copolymerizable groups and at least one of these groups is present in a side chain. B represents a monomer unit obtained by copolymerizing ethylenically unsaturated copolymerizable monomers. R₁₃ represents a hydrogen atom, a lower alkyl group or an aralkyl group.
Q represents a single bond, or an alkylene groups, a phenylene group, an aralkylene group,
Wherein L represents an alkylene, arylene or aralkylene group and R is an alkyl group. G represents

X⊖ and R ₁₄ , R ₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂o and R₂₁ may be the same or different and may be substituted and each represents a hydrogen atom, an alkyl, aryl or aralkyl group. X ⁰ represents an anion. Two or more groups selected from Q, R₁₄ , R₁₅ and R₁6 or Q, R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁ may be bonded to form a ring structure together with the nitrogen atom.
x, y and z each represents molar percentage, x ranges from 0 to 60, y from 0 to 60 and z from 30 to 100.
The foregoing general formula (VIII) will hereunder be explained is more detail. Examples of monomers from which A is derived are divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol dimethacrylate and tetramethylene glycol dimethacrylate and particularly divinylbenzene and ethylene glycol dimethacrylate are preferred.
A may comprise at least two of the foregoing monomer units.
Examples of ethylenically unsaturated monomer from which B is derived include ethylene, propylene, 1-butene, isobutene, styrene, a -methylstyrene, vinyltoluene, monoethylenically unsaturated esters of aliphatic acids (e.g., vinyl acetate and allyl acetate), esters of ethylenically unsaturated monocarboxylic acids or dicarboxylic acids (e.g., methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, n-butyl acrylate, n-hexyl acrylate and 2-ethylhexyl acrylate), monoethylenically unsaturated compounds (e.g., acrylonitrile), or dienes (e.g., butadiene and isoprene). Particularly preferred are styrene, n-butyl methacrylate and cyclohexyl methacrylate. B may comprise two or more of the foregoing monomer units.
R₁₃ preferably represents a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms such as a methyl, ethyl, n-propyl, n-butyl, n-amyl or n-hexyl group or an aralkyl group such as a benzyl group and particularly preferred are a hydrogen atom and a methyl group.
Q preferably represents a divalent optionally substituted alkylene group having 1 to 12 carbon atoms such as a methylene, ethylene or hexamethylene group, an optionally substituted arylene group such as a phenylene group, or an optionally substituted aralkylene group having 7 to 12 carbon atoms such as
CH =-
C H ₂ C H₂- and groups represented by the following formulas are also preferred:
Wherein L preferably represents an optionally substituted alkylene group having 1 to 6 carbon atoms, or an optionally substituted arylene group or an optionally substituted aralkylene group having 7 to 12 carbon atoms, more preferably an optionally substituted alkylene group having 1 to 6 carbon atoms. R is preferably an alkyl group having 1 to 6 carbon atoms.
G represents

X ⊖ and R₁₄, R ₁₅ , R₁₆, R₁₇ , R₁₈, R₁₉, R₂₀ and R₂₁ may be the same or different and each represents a hydrogen atom, an alkyl having 1 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms. These alkyl, aryl and aralkyl groups include substituted alkyl, aryl and aralkyl groups.
Examples of alkyl groups include such unsubstituted alkyl groups as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, n-amyl, iso-amyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl and n-dodecyl groups. The number of carbon atoms of the alkyl group preferably ranges from 1 to 16 more preferably 4 to 10.
Examples of substituted alkyl groups are alkoxyalkyl groups such as methoxy methyl, methoxyethyl, methoxybutyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, butoxyethyl, butoxypropyl, butoxybutyl and vinyloxyethyl; cyanoalkyl groups such as 2-cyanoethyl, 3-cyanopropyl and 4-cyanobutyl; halogenated alkyl groups such as 2-fluoroethyl, 2-chloroethyl and 3-fluorepropyl; alkoxycarbonylalkyl groups such as ethoxycarbonylmethyl; allyl group, 2-butenyl group and propargyl.
Examples of aryl groups include such unsubstituted aryl groups as phenyl and naphthyl groups; such substituted aryl groups as alkylaryl groups (e.g., 2-methylphenyl, 3-methylphenyl, 4-methylphenyl. 4-ethylphenyl, 4-isopropylphenyl and 4-t-butylphenyl); alkoxyaryl groups (e.g., 4-methoxyphenyl, 3-methoxyphenyl and 4-ethoxyphenyl); and aryloxyaryl groups (e.g., 4-phenoxyphenyl). The nubmer of carbon atoms of the aryl group preferably ranges from 6 to 14, more preferably 6 to 10. Particularly preferred is a phenyl group.
Examples of aralkyl groups include unsubstituted aralkyl groups such as benzyl, phenethyl, diphenylmethyl and naphthylmethyl; substituted aralkyl groups such as alkylaralkyl groups (e.g., 4-methylbenzyl, 2,5-dimethylbenzyl and 4-isopropylbenzyl), alkoxyaralkyl groups (e.g., 4-methoxybenzyl and 4-ethoxybenzyl), cyanoaralkyl groups (e.g., 4-cyanobenzyl), perfluoroalkoxyaralkyl groups (e.g., 4-pentafluoropropoxybenzyl and 4-undecafluorohexyloxybenzyl) and halogenoaralkyl groups (e.g., 4-chlorobenzyl, 4-bromobenzyl and 3-chlorobenzyl). The number of carbon atoms of the aralkyl group preferably ranges from 7 to 15 and more preferably 7 to 11. Among these, benzyl and phenethyl groups are particularly preferred.
R₁₄, R₁₅ and R,₆ each preferably represents an alkyl or aralkyl group, in particular they represent alkyl groups whose total number of carbon atoms ranges from 12 to 30.
R ₁₇ to R₂₁ each preferably represents a hydrogen atom or an alkyl group.
X⊖ epresents an anion such as a hydroxide ion, a halogen ion (e. g., chloride or bromide ion), an alkyl- or arylsulfonate ion (e.g., a methanesulfonate, ethanesulfonate, benzenesulfonate or p-toluenesulfonate ion), an acetate ion, a sulfate ions and a nitrate ion. Particularly preferred are chloride, acetate and sulfate ions.
At least two groups selected from Q and R₁₁ to R₁₅ may preferably be bonded to form a ring structure together with the nitrogen atom. Examples of such rings preferably include pyrrolidine, piperidine, morpholine, pyridine, imidazole and quinuclidine rings. Particularly preferred are pyrrolidine, morpholine, piperidine, imidazole and pyridine rings.
At least two groups selected from Q and R₁₇ to R₂₁, may be bonded to form a ring structure together with the nitrogen atom. Particularly preferred are 5- or 6-membered ring structures.
The basic anion-exchange resins of the invention may comprise tw o or more of the foregoing monomer units:
x ranges from 0 to 60 mole%, preferably 0 to 40 mole%, and more preferably 0 to 30 mole%. y ranges from 0 to 60 mole%, preferably 0 to 40 mole% and more preferably 0 to 30 mole%. z ranges from 30 to 100 mole%, preferably 40 to 95 mole% and more preferably 50 to 85 mole%.
Among the compounds represented by formula (VIII), particularly preferred are those represented by the following general formula (IX):
In the formula, A, B, x, y, z, R₁₃ to R₁₆, and X⊖ are the same as those in the general formula (VIII).
More preferred are those represented by formula (IX) in which all of the groups R₂ to R₄ are alkyl groups whose total number of carbon atoms ranges from 12 to 30.
Specific examples of the basic anion-exchange resins of the present invention represented by the general formula (VIII) will be listed below, but the compounds of this invention are not restricted to these specific examples.
In the present invention, various commercially available resins may be used as the basic anion-exchange resins. specific examples thereof include Amberlite IRA-410, IRA-411, IRA-910, IRA-400, IRA-401, IRA-402, IRA-430, IRA-458, IRA-900, IRA-904 and IRA-938 (all these being available from Rohm & Haas Co., Ltd.); DIAION SA 10A, SA 12A, SA 20A, SA 21A, PA 306, PA 316, PA 318, PA 406, PA 412 and PA 418 (all these being available from MITSUBISHI CHEMICAL INDUSTRIES LTD.) and EPOLUS K-70 (available from MIYOSHI FAT & OIL CO., LTD.).
Moreover, they may be synthesized in accordance with the following Preparation Examples.

General Method for Preparation

The anion-exchange resins of this invention can be synthesized by quaternarizing a substantially water-insoluble resin having groups capable of being quaternarized with a tertiary amine or a tertiary phosphine (hereunder referred to as a "precursor resin") with a tertiary amine or a tertiary phosphine to introduce cations. The precursor resins may be prepared by a variety of methods as disclosed in J.P. KOKAI No. 59-39347, U.S. Patent Nos. 2,874,132; 3,297,648; 3,549,562; 3,637,535; 3,817,878; 3,843,566; 2,630,427 and 2,630,429; German Patent No. 1,151,127 and J.P. KOKOKU Nos. 32-4143, 46-19044, 46-20054, 53-5294, 33-2796 and 33-7397 or methods similar thereto.
The introduction of cationic groups into the precursor resin by quaternarization with a tertiary amine or phosphine can be carried out by using the foregoing precursor resin and a tertiary amine or phosphine according to methods as disclosed in J.P. KOKAI No. 59-39347; U.S. Patent Nos. 2,874,132; 3,297,648; 3,549,562; 3,637,535; 3, 817,878; 3,843,566; 2,630,327; 2,630,429; German Patent No. 1,151,127 and J.P. KOKOKU Nos. 32-4143, 46-19044; 46-20054, 53-5294; 33-2796 and 33-7397 or methods similar thereto.
Alternatively, the anion-exchange resin of this invention may also be obtained by using a substantially water-insoluble monomer having a copolymerizable ethylonically unsaturated group and a quaternary ammonium or phosphonium group in the foregoing methods for synthesizing the precursor resins or the methods similar thereto to form a resin.
Further, the anion-exchange resin of this invention may be obtained by using a monomer mixture of a substantially water-insoluble copolymerizable monomer having a quaternary ammonium or phosphonium group and an ethylenically unsaturated group and a substantially water-insoluble copolymerizable monomer having a group capable of being quaternarized with an amine or phosphine and an ethylenically unsaturated group in the foregoing methods for synthesizing the precursor resin or the methods similar thereto to obtain a resin and then introducing cations into the precursor resin according to the foregoing methods for quaternarization with a tertiary amine or phosphine or the methods similar thereto.

Preparation Example 1:

Preparation of poly(divinylbenzene-co-chloromethylstyrene)

To a 3z three-necked flask equipped with a stirrer, a thermometer and a cooling tube, there were introduced, at room temperature, 1500g of water, 2.5g of polyvinyl alcohol (available from The Nippon Synthemical Chemical Industry Co., Ltd. under the trade name of GOSENOL) and 80g of sodium chloride and they were sufficiently stirred to dissolve. To the solution, there was added, at room temperature, a solution of 206g of chloromethylstyrene (available from Seimi Chemical Co., Ltd. under the trade name of CMS-AM), 19.5g of divinylbenzene, and 4.0g of benzoyl peroxide in 200g of toluene and the solution was stirred for one hour at 110 rpm in a nitrogen gas stream. The temperature of the solution was raised to 70°C to perform the reaction for 7 hours, followed by filtering off the resulting resin spheres, immersing the resin in 5a of warm water of 50°C to subject it to ultrasonic washing for 30 min. The resin was likewise washed with 29 of methanol, 2l of acetone and 2l of ethyl acetate, dried at 100°C under a reduced pressure to obtain 221.2g of spherical resin particles having a particle size of not more than 1 mm. The resin was subjected to elemental analysis to determine the content of chlorine and it was confirmed that the content was 5.89 x 10^-3 mole/g resin.

Preparation of Poly(divinylbenzene-co-tributylammonio-methylstyrene chloride) (Compound 3)

20g of poly(divinylbenzene-co-chloromethylstyrene) spherical particles prepared above was weighed and put in a 500 ml 3-necked flask equipped with a stirrer, a thermometer and a cooling tube followed by adding 40g of isopropyl alcohol, 40g of dimethylacetamide and 40g of tributylamine and swelling the resin for 7 hours at room temperature with stirring. The resin was heated to 85°C to react it for 8 hours under refluxing. Then, the reaction system was cooled to room temperature and solid contents (spherical resin particles) were filtered off. The resin spheres were immersed in warm water of 50°C to perform ultrasonic washing for 30 min., followed by repeating ultrasonic washing using 2£ of methanol, 2£ of acetone, 2£ of ethyl acetate and 2l of acetone in this order for every 20 min. and drying at 120°C under a reduced pressure to obtain 38.6g of spherical resin particles. The chloride ion content was 2.70 x 10^-3 (mole/g resin).
The chloride ion content was determined by swelling the ground resin in 1N sodium nitrate solution and titrating the solution with 0. 1N silver nitrate.

Preparation Example 2:

Preparation of N-vinylbenzyl-N,N,N-trihexylammonium chloride

54.9g (0.36 mole) of chloromethylstyrene, 80.7g (0.30 mole) of tri-n-hexylamine, 0.5g of nitrobenzene as a polymerization inhibitor and 400 ml of acetonitrile were fed to 1l 3-necked flask and they were refluxed under heating for 7 hours with stirring.
After cooling to room temperature, the solution was washed with 500 ml of n-hexane several times to remove unreacted chloromethylstyrene. The solution was concentrated to precipitate crystals and the crystals were recrystallized from 500 ml of ethyl acetate to obtain 103.89g of intended N-vinylbenzyl-N,N,N-trihexylammonium chloride as white crystals (yield: 82.1%). The molecular structure of the resultant compound was confirmed by 'H-NMR and elemental analysis.

Preparation of Poly(divinylbenzene-co-trihexylammoniomethylstyrene chloride) (Compound 4)

288g of water and 143.5g (0.34 mole) of N-vinylbenzyl-N,N,N-trihexylammonium chloride were introduced into a 3l 3-necked flask equipped with a stirrer, a thermometer and a cooling tube to let sufficiently absorb water to thus obtain an oily substance. To the oily substance, there were added 7.8g (0.06 mole) of divinylbenzene and 3.0g of azobisisobutyronitrile (available from WACO JUNYAKU CO., LTD. under the trade name of V-60) and the mixture was stirred to dissolve. Further, a solution of 1080g calcium chloride and 2.3g of polyvinyl alcohol (the same as that used above) in 1152g of water was added to the resultant solution and the solution was stirred at room temperature for 30 min. at 135 rpm in a nitrogen gas stream. the temperature of the solution was raised to 70 C and was stirred for 6 hours.
The solution was cooled to room temperature, the solid contents were filtered off and they were subjected to ultrasonic washing in 2P of distilled water maintained at 50°C for 30 min. Then, the ultrasonic washing was repeated using 2l of methanol, 2l of acetone and 2l of ethyl acetate as solvents and the solid was dried at 100°C under a reduced pressure to obtain 122.6g of spherical particles. The chlorine content thereof was 1.8 x 10-³ (mole/g resin).

Preparation Example 3:

Preparation of Poly(divinylbenzene-co-trihexylammoniomethylstyrene chloride-co-chloromethylstyrene)

There were introduced, into a 5 f 3-necked flask equipped with a stirrer, a thermometer and a cooling tube, 360g of water and 84.4g (0.2 mole) of N-vinylbenzyl-N,N,N-trihexylammonium chloride to let sufficiently absorb water to thus obtain an oily substance. To the oily substance, there were added 10.4g (0.08 mole) of divinylbenzene, 18.3g (0.12 mole) of chloromethylstyrene (the same as that used above) and 2.9g of azobisisobutyronitrile (the same as that used above) and the mixture was stirred to dissolve. To the solution, there was added a solution of 864g of calcium chloride and 2.0g of polyvinyl alcohol (the same as that used above) in 930g of water followed by stirring the mixture at room temperature, for 30 min. at 120 rpm in a nitrogen gas stream. The temperature of the solution was raised to 80°C and the solution was stirred for 7 hr.
The solution was cooled to room temperature followed by filtering off the solid contents obtained and subjecting them to ultrasonic washing in 2l of distilled water maintained at 50°C for 30 min. The ultrasonic washing was repeated using 29 each of methanol, acetone and ethyl acetate as solvents and the solid contents were dried at 100°C under a reduced pressure to obtain 95.2g of spherical particles. The resultant resin was analyzed by elemental analysis and it was found that the total chlorine content thereof was 2.78 x 10-³ (mole/g resin). In addition, the resin was titrated to obtain chloride ion content and it was found to be 1.65 x 10-³ (mole/g resin).

Preparation of Poly(divinylbenzene-co-tributylammoniomethylstyrene Chloride-co-trihexylammoniamethylstyrene Chloride) (Compound 51)

There was introduced 75g of the spherical particles of poly(divinylbenzene-co-trihexylammoniomethylstyrene chloride-co-chloromethylstyrene) into an 1 l3-necked flask provided with a stirrer, a thermometer and a cooling tube and 100 ml of isopropyl alcohol, 100 ml of acetonitrile and 150g of tributylamine were added thereto to swell the polymer at room temperature for 7 hr. with stirring. The solution was heated to 80°C to cause a reaction for 9 hr. with refluxing the solvent. Thereafter, the reaction system was cooled to room temperature and the resultant solid contents (spherical resin particles) were filtered off. The spherical resin was immersed in warm water of 50°C to carry out ultrasonic washing for 30 min. and it was repeated using 2l each of methanol, acetone, ethyl acetate and acetone in this order.

Preparation Example 5:

Preparation of Poly(divinylbenzene-co-chloromethylstyrene)

There were introduced, at room temperature, 3000g of water, 5.0g of polyvinyl alcohol (available from The Nippon Synthemical Chemical Industry Co., Ltd. under the trade name of GOSENOL) and 160g of sodium chloride into a 5R 3-necked flask equipped with a stirrer, a thermometer and a cooling tube and the mixture was sufficiently stirred to dissolve. To the solution, there was added a solution of 412g of chloromethylstyrene (available from SEIMI Chemicals Co., Ltd. under the trade name of CMS-AM), 43.4g of divinylbenzene and 8.0g of benzoyl peroxide in 500g of toluene at room temperature, followed by stirring the solution for 30 min. at 120 rpm in a nitrogen gas stream. raising the temperature to 70°C and reacting for 7 hr. After the reaction, the resulting spherical resin particles were filtered off, followed by immersing them in 5l of warm water of 50°C to perform ultrasonic washing for 30 min., likewise repeating the ultrasonic washing using 2£ each of methanol, acetone and ethyl acetate and drying at 100°C under a reduced pressure to obtain 440g of spherical resin particles having a particle size of not more than 1 mm. The resin was subjected to elemental analysis and the chlorine content thereof was found to be 5.85 x 10^-3 mole/g resin.

Preparation of Poly(divinylbenzene-co-trimethylammoniomethylstyrene chloride-co-tributylammoniomethylstyrene chloride) (Compound 49)

20g of poly(divinylbenzene-co-chloromethylstyrene) spherical particles were introduced into a 500 ml 3-necked flask equipped with a stirrer, a thermometer and a cooling tube, and 70g of isopropyl alcohol, 30g of dimethylformamide and 40g tributylamine were added thereto to swell the resin at room temperature for 30 min. with stirring. The reaction system was heated to 80°C and the reaction was continued for 6 hr. with refluxing the solvent. Then, the reaction system was cooled to room temperature, the resulting solid contents was filtered off, followed by adding 40g of 30% aqueous trimethylamine solution, reacting at room temperature for 2hr., raising the temperature to 80°C by heating for one hour and filtering off the resin particles in the system. The spherical resin was sufficiently washed with running warm water of 50°C , ultrasonic washing was performed for every 30 min. using 2£ each of methanol, acetone, ethyl acetate and acetone in this order and the resin was dried at 120°C under a reduced pressure to obtain 30.0g of spherical resin particles. The chloride ion content thereof was 3.1 x 10^-3 (mole/g resin).
The chloride ion content was determined by swelling the ground resin in 1N sodium nitrate solution and titrating the solution with 0. 1N silver nitrate.

Preparation Example 6:

There were introduced, at room temperature, 360g of water and 168.9g (0.40 mole) of N-vinylbenzyl-N,N,N-trihexylammonium chloride to let sufficiently absorb water to thus obtain an oily substance. To the oily substance, there were added 5.2g (0.04 mole) of divinylbenzene, 9.2g (0.06 mole) of chloromethylstyrene and 4.0g of benzoyl peroxide and further a solution of 1350g of calcium chloride in 1,000g of water and a solution of 2.9g of polyvinyl alcohol (the same as that used above) in 440g of water, with stirring. The solution was stirred at room temperature, at 150 rpm in a nitrogen gas stream for 30 min., then heated to 70°C and further stirred for 6 hr.
The solution was cooled down to room temperature, the resulting solid contents were filtered off and were subjected to ultrasonic washing for 30 min. in 2l of distilled water maintained at 50°C . Then, the washing was repeated using, as solvents, 2l each of methanol, acetone and ethyl acetate and the solid was dried at 100°C under a reduced pressure to obtain 176.8g of spherical resin particles (chloride ion content: 2.1 x 10-³ mole/g resin).

Preparation of Poly(divinylbenzene-co-trimethylammoniomethylstyrene chloride-co-trihexylammoniomethylstyrene) (Compound 48)

150g of the poly(divinylbenzene-co-trihexylammoniomethyl- chloride-co-chloromethylstyrene) obtained above was introduced into a 2£ 3-necked flask equipped with a stirrer, a thermometer and a cooling tube and 300 ml of dichloroethane was added thereto at room temperature to swell the resin for 30 min. Then, 500 ml of 30% aqueous trimethylamine solution was added, followed by allowing to stand for one hour to swell and reacting at room temperature for 2 hr. with stirring. Thereafter, the system was heated to 80°C to get out dichloroethane from the system by azeotropy. 500 ml of water was added in three portions during heating to prevent drying of the resin. After continuing the removal of the solvent until dichloroethane was not distilled by azeotropy, the resultant solid contents were filtered off and washed with running water sufficiently. Then, the solid was subjected to ultrasonic washing in 3l of warm water of 50°C for 30 min., followed by repeating the washing using 2£ each of methanol, acetone, ethyl acetate and acetone for every 30 min. and drying the solid at 120°C under a reduced pressure to obtain 147.2g of spherical resin particles. The chloride ion content thereof was 3.0 x 10-' (mole/g).
In the general formula (VIII), G preferably represents
from the viewpoint of selective removal of iodide ions and more preferably G represents such a functional group wherein the total carbon atom number of R14 to R16 is not less than 12. Specifically, preferred are Compounds (3) to (5), (12), (19), (20), (23), (24), (28). (29), (32), and (44) to (49).
In the method of this invention, the bleaching process is performed while a part or whole of a bleaching solution is brought into contact with an anion-exchange resin. The contact between the bleaching solution and the anion-exchange resin can be carried out by, for instance, packing an anion-exchange resin, in a column and incorporating it into a circulating pump of a fixing bath (e.g., a bleaching or bleach-fixing bath); or charging it into a subtank separately disposed and continuously or intermittently circulating a fixing solution from the fixing bath to the subtank. Alternatively, the contact can be performed by a method comprising packaging an anion-exchange resin in a bag of fine mesh net and immersing the same in the bath for fixing.
In the present invention, the processing solution for fixing (processing solution having fixing ability) includes fixing solutions and bleach-fixing solutions, particularly it is preferably a bleach-fixing solution.
The method may be a continuous or batchwise one, preferably a continuous method. In particular, a continuous processing using an automatic developing machine to easily process a large amount of light-sensitive materials.
The continuous processing herein means a processing in which a processing solution is supplemented while the processing is continuously or intermittently performed for a long time period. The amount of the processing solution (replenisher) is determined depending on, for instance, area of the light-sensitive materials to be processed and processing time.
In addition, the method can be applied to a so-called regeneration system in which a solution obtained by bringing the overflow (fixing processing solution) from a fixing bath into contact with an anion-exchange resin is reused as a replenisher.
In addition, the present invention can be applied to so-called batch system in which a certain amount of light-sensitive material is processed with a constant amount of a processing solution without replenishment. In this case, the processing solution can be in contact with an anion-exchange resin during fixing process by, for instance, immersing the resin in the fixing processing solution.
The amount of the processing solution having fixing ability (fixing processing solution) to be brought into contact with the anion-exchange resins is 20 to 2000 liters and preferably 20 to 1000 liters per liter of the anion-exchange resins.
"The amount of the processing solution per liter of the anion-exchange resin" herein means the cumulative amount of the fixing processing solution supplemented during a continuous processing of light-sensitive materials per liter of the resin and if a replenisher is supplemented in the amount defined above, the resin should be replaced with a fresh one.
In the case of a batch system, the amount of a fixing processing solution per liter of a resin which is brought into contact with the resin, means the cumulative amount of the solution used until the resin is exchanged. For instance, if 10i of the processing solution per batch is used, the resin is replaced with a new one after at least two batches (20l of the solution) are contact therewith. In a batch system, the amount of the fixing processing solution to be in contact with the resin preferably ranges from 20 to 200l .
In a usual processing, about 10 to 2,000d of light-sensitive materials are processed with about 5 to 20l of the processing solution. Moreover, the amount of the processing solution to be replenished varies depending on the kinds of light-sensitive materials and processing solutions and their formulations, but it preferably ranges from about 50 to 2,000 ml, more preferably about 100 to 500 ml per 1m² of the light-sensitive material.
In general, supplementation of the fixing and bleach-fixing solutions is performed depending on area of the light-sensitive materials to be processed, but if the amount of the replenisher is saved, the rate of fixing is lowered because of the accumulation of substances dissolved out from the light-sensitive material, as a result, the rate of desilvering is lowered and if the processing time is constant, insufficient fixing, i.e., insufficient desilvering is caused. However, in the method of this invention, such delay in fixing can be prevented since the foregoing processing with an anion-exchange resin is performed and a replenisher-saved and rapid processing can be achieved.
The light-sensitive materials to be processed by the method of this invention includes emulsion layers containing the aforesaid silver iodide. Other constructions thereof will be described below.

Treatment of Emulsion Layer and General Additives

The silver halide emulsions as used herein are subjected to physical and/or chemical ripening and are spectrally sensitized. Additives used in such processes are disclosed in Research Disclosure (RD), Vol. 176, No. 17643 (December, 1978) and ibid, Vol. 187, No. 18716 (November, 1979). The relevant passages are summarized in the following Table.
Photographic additives usable in the invention are also disclosed in the same articles (two Research Disclosures) and likewise the relevant passages are listed in the following Table.
Color Couplers
The color light-sensitive materials to be processed in the present invention may contain a color coupler. "Color coupler(s)" herein means a compound capable of forming a dye through coupling reaction with an oxidized form of an aromatic primary amine developing agent. Typical examples of useful color couplers are naphthol or phenol type compounds, pyrazolone or pyrazoloazole type compounds, and linear or heterocyclic ketomethylene compounds. Cyan, magenta and yellow color couplers which may be used in the present invention are disclosed in the patents cited in Research Disclosure No. 17643 (December, 1978) VII-D; and ibid, No. 18717 (November, 1979).
The color couplers to be incorporated into the light-sensitive materials are preferably made non-diffusible by imparting thereto ballast groups or polymerizing them. 2-Equivalent couplers which are substituted with coupling elimination groups are more preferable than 4-equivalent couplers in which a hydrogen atom is in a coupling active site, because the amount of coated silver can be decreased. Furthermore, couplers in which a formed dye has a proper diffusibility, non-color couplers, DIR couplers which release a development inhibitor through coupling reaction or couplers which release a development accelerator during coupling reaction may also be used.
Magenta couplers usable in the present invention include couplers of an oil protect type of indazolone, cyanoacetyl, or preferably pyrazoloazole such as 5-pyrazolone and pyrazolotriazol type ones. Among 5-pyrazolone type couplers, couplers whose 3-position is substituted with an arylamino or acylamino group are preferred from the viewpoint of color phase and color density of the formed dye. Typical examples thereof are disclosed in U.S. Patent Nos. 2,311,082; 2,343,703; 2,600,788; 2,908,573; 3,062,653; 3,152,896 and 3,936,015. An elimination group of the 2-equivalent 5-pyrazolone type couplers is preferably a nitrogen atom elimination group described in U.S. Patent No. 4,310,619 and an arylthio group described in U.S. Patent No. 4,351,897. The 5-pyrazolone type coupler having ballast groups described in European Patent No. 73,636 provide high color density.
As examples of pyrazoloazole type couplers, there may be named pyrazolobenzimidazoles described in U.S. Patent No. 3,369,879, preferably pyrazolo(5,1-c)(1,2,4)triazoles described in U.S. Patent No. 3,725,067, pyrazolotetrazoles described in Research Disclosure No. 24230 (June, 1984) and pyrazolopyrazoles described in European Patent No. 119,741 is preferred on account of small yellow minor absorption of formed dye and light fastness. Pyrazolo(1,5-b)(1,2,4)triazole described in European Patent No. 119,860 is particularly preferred.
Cyan couplers which may be used in the present invention include naphthol or phenol type couplers of an oil protect type. Typical naphthol type couplers are disclosed in U.S. Patent No. 2,474,293. Typical preferred 2-equivalent naphtholic couplers of oxygen atom elimination type are disclosed in U.S. Patent Nos. 4,052,212; 4,146,396; 4,228,233; and 4,296,200. Exemplary phenol type couplers are disclosed in U.S. Patent Nos. 2,369,929; 2,801,171; 2,772,162 and 2,895,826. Cyan couplers which are resistant to humidity and heat are preferably used in the present invention. Examples thereof are phenol type cyan couplers having an alkyl group having not less than two carbon atoms at a metha-position of a phenolic nucleus as disclosed in U.S. Patent No. 3,772,002; 2,5-diacylamino substituted phenol type couplers as disclosed in U.S. Patent Nos. 2,772,162; 3,758,308; 4,126. 396; 4,334,011 and 4,327,173; DEOS No. 3,329,729; and Japanese Patent Application Serial (hereunder referred to as "J.P.A.") No. 58-42671; and phenol type couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position as disclosed in U.S. Patent Nos. 3,446,622; 4,333,999; 4,451,559; and 4,427,767.
A typical yellow coupler capable of being used in the present invention is an acylacetamide coupler of an oil protect type. Examples of these are disclosed in U.S. Patent Nos. 2,407,210; 2,875,057; and 3,265,506. 2-Equivalent yellow couplers are preferably used in the present invention. Typical examples thereof include the yellow couplers of an oxygen atom elimination type disclosed in U.S. Patent Nos. 3,408,194; 3,447,928; 3,933,501 and 4,022,620, or the yellow couplers of a nitrogen atom elimination type disclosed in J.P. KOKOKU No. 55-10739; U.S. Patent Nos. 4,401,752; and 4,326,024, Research Disclosure No. 18053 (April, 1979), U.K. Patent No. 1,425,020, DEOS Nos. 2,219,917; 2,261,361; 2,329,587 and 2,433,812. Alpha-pivaloyl acetanilide type couplers are excellent in fastness, particularly light fastness, of the formed dye. a -benzoyl acetanilide type couplers yield high color density.
Graininess may be improved by using together a coupler which can form a dye moderately diffusible. As such dye-diffusing couplers, some magenta couplers are specifically described in U.S. Patent No. 4. 366,237 and U.K. Patent No. 2,125,570 and some yellow, magenta and cyan couplers are specifically described in European Patent No. 96,570 and DEOS No. 3,234,533.
Dye-forming couplers and the aforesaid special couplers may be a dimer or a higher polymer. Typical examples of polymerized dye-forming couplers are described in U.S. Patent Nos. 3,451,820 and 4,080. 211. Examples of polymerized magenta couplers are described in U.K. Patent No. 2,102,173 and U.S. Patent No. 4,367,282.
In order to meet properties required for light-sensitive materials, two or more couplers may be used together in a single light-sensitive layer, or the same coupler may be introduced in two or more different light-sensitive layers.
The standard amount of the color couplers to be used is 0.001 to 1 mole and preferred amount thereof is 0.01 to 0.5 mole for yellow couplers, 0.003 to 0.3 mole for magenta couplers and 0.002 to 0.3 mole for cyan couplers per mole of light-sensitive silver halide.
The couplers used in the invention can be introduced into the color light-sensitive materials by a variety of known methods for dispersion. Examples of high boiling point organic solvents used in the oil-in-water dispersion method are disclosed in U.S. Patent No. 2,322,027. Specific examples of processes, effects and latexes for impregnation, for latex dispersion method are, for instance, disclosed in U.S. Patent No. 4,199,363 and DE OLS Nos. 2,541,274 and 2, 541,230.

Substrate

The photographic light-sensitive materials to be processed by the present invention are applied to the surface of a flexible substrate such as a plastic film (e.g., cellulose nitrate, cellulose acetate or polyethylene terephthalate) or paper; or a rigid substrate such as a glass plate. Substrates and methods for applying the photographic light-sensitive materials thereto are detailed in Research Disclosure, Vol. 176, No. 17643, Item XV (p. 27) and XVII (p. 28) (December, 1978).
Typical examples of the photographic light-sensitive materials to be processed by the method of the present invention include color negative films for general use or motion picture, color reversal films for slide or television, color paper, color positive films, color reversal paper, direct positive color light-sensitive materials, monochromatic films, monocromatic paper x-ray films and light-sensitive materials for printing.

Development Processing

The method of this invention comprises a variety of combination of the processing processes and specific examples thereof are as follows:

(i) Development - Bleaching - fixing - Water Washing - Drying
(ii) Development - Bleaching - fixing - Water Washing - Stabilization - Drying
(iii) Development - Bleaching - fixing - Stabilization - Drying
(iv) Development - Bleach-fixing - Water Washing - Drying
(v) Development - Bleach-fixing - Stabilization - Drying
(vi) Development - Bleach-fixing - Water Washing - Stabilization - Drying
(vii) Development - Bleaching - Bleach-fixing - Water Washing - Drying
(viii) Development - Bleaching - Bleach-fixing - Water Washing - Stabilization - Drying

In this respect, it is also possible in the foregoing processes. to carry out water washing process between the development and bleaching or bleach-fixing processes; or between the bleaching and fixing processes. Each processing may be performed according to any manners such as a single bath processing, a multistage countercurrent system or multistage direct flow system. The foregoing development processing may comprise reversal color development process. For instance, it comprises monochromatic development - water washing - reversal - color deveolopment processes.

Development

The color developer used to develop the light-sensitive materials is preferably an aqueous alkaline solution containing, as a principal component, an aromatic primary amine type color developing agent. Although aminophenol type developing agents are also useful as the color developing agent, but preferred are p-phenylenediamine type compounds whose typical examples are 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-u-amino-N-ethyl-N- β -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-E -methanesulfonamido-ethylaniline, and 3-methyl-4-amino-N-ethyl-N-E -methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. These diamines in the form of salts are in general more stable than those in the free state and, therefore, they are preferably used in the form of salts.
The color developer in general contains pH buffering agents such as carbonates, borates or phosphates or alkali metals; development inhibitors such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds; or antifoggants. The color developer may further comprise, according to need, various kinds of preservatives such as hydroxylamine, diethylhydroxylamine, sulfites and compounds disclosed in J.P.A. No. 61-280792; organic solvents such as triethanolamine and diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts and amines; fogging agents such as dye-forming couplers, competing couplers and sodium borohydride; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; thickening agents; a variety of chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid; and anti-oxidizing agents as disclosed in DE OLS No. 2,622,950.
In addition, if the reversal processing is performed, the photographic light-sensitive materials are in general subjected to monochromatic development prior to the color development. In such a monochromatic developer, there may be used any known monochromatic developing agents, for instance, dihydroxybenzenes such as hydroquinone; 3-pyrazolidones such as 1-phenyl-3-pyrazolidone; and aminophenols such as N-methyl-p-aminophenol, which may be used alone or in combination.
The amount of the color developer and the monochromatic developer to be replenished generally varies depending on the kinds of the color photographic light-sensitive materials to be processed and it is in general not more than 3 liters per 1 rd of the light-sensitive material to be processed. However, it can be reduced to not more than 500 ml by reducing the amount of bromide ions present in the replenisher therefor. When the amount of the replenisher is reduced, the area of the opening of the processing bath should be limited to a small value to prevent the evaporation of the solution and the oxidation thereof with air. Alternatively, the amount of the replenisher may be reduced by utilizing a means for suppressing the accommodation of the bromide ions in the developer.

Bleaching, Fixing

Subsequently, the color developed photographic emulsion layer is generally processed with a bleach-fixing solution. The bleaching treatment and the fixing treatment may be performed separately or simultaneously. In this respect, the developed light-sensitive materials may be first bleached and then bleach-fixed for the purpose of achieving a rapid processing. It may be fixed prior to the bleach-fixing treatment or it may be bleach-fixed and then bleached according to purposes.
As the bleaching agents, there may be used, for instance, compounds of polyvalent metals such as iron(III), cobalt(III), chromium(IV) and copper(II); peracids; quinones; and nitroso compounds. Typical examples thereof include ferricyanides; bichromates; organic complexes of iron(III) or cobalt(III), such as complexes of organic acids, e.g., aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid and organic acids such as citric acid, tartaric acid or malic acid; persulfates; hydrobromides; manganates; and nitrosophenol. Among these, ferric aminopolycarboxylates such as ferric et hylenediaminetetraacetate and persulfates are preferably used on account of rapid processing and prevention of environmental pollution. In addition, ferric complexes of aminopolycarboxylic acid are particularly preferred in both separate bleaching solutions and bleach-fixing solutions in one bath.
Examples of fixing agents are thiosulfates, thiocyanates, thioether type compounds, thioureas and a large amount of iodides, but in general thiosulfates sulfates are used and particularly ammonium thiosulfate is most widely used. Preferred preservatives for the bleach-fixing solution and the fixing solution are sulfites, bisulfites and carbonylbisulfite adducts.
Among the aforementioned processing solutions used in the desilvering process, the amount of the processing solution having fixing ability to be replenished is preferably not less than 50 to 2000 ml per ld of the processed light-sensitive material and more preferably 100 to 500 ml.

Water Washing and Stabilization

It is common that the silver halide color photographic light-sensitive materials to be processed by the present invention are subjected to water washing and/or stabilization processes after the desilvering process.
The amount of washing water in water washing process can widely be established depending on a variety of conditions such as characteristics of the light-sensitive materials to be processed (for instance, materials used such as couplers), applications, the temperature of the washing water, the number of washing tanks (step number), and the manners of the replenishment, for instance, direct flow system and countercurrent flow system. Among these, the relation between the amount of water and the number of water washing tanks in the multistage countercurrent flow system can be obtained by the method disclosed in Journal of the Society of Motion Picture and Television Engineers, 1955, May, Vol. 64, p. 248-253.
Although, the multistage countercurrent flow system disclosed in the foregoing article makes it possible to extremely reduce the amount of washing water, the retention time of water in the tanks increases and as a result bacteria proliferates therein which leads to the formation of floating substances and the adhesion of the substances to the processed light-sensitive materials.
In order to solve such problems in the processing of color light-sensitive materials, a method for reducing the amount of calcium and magnesium, in washing water and/or the replenisher therefor disclosed in J.P.A. No. 61-131632 can be effectively adopted in the invention. Alternatively, the problems can also be solved by utilizing isothiazolone compounds and thiabendazoles disclosed in J.P. KOKAI No. 57-8542; such chlorine type antibacterial agents as sodium chlorinated isocyanurates; or other antibacterial agents such as benzotriazoles disclosed in "BOKIN BOBAIZAI NO KAGAKU (Chemistry of Antibacterial and Antifungus Agents)", Hiroshi HORIGUCHI; "BISEIBUTSU NO MEKKIN, SAKKIN AND BOBAI GIJUTSU (Sterilization, Pasteurization and Mold Controlling Techniques)", edited by Sanitary Engineering Society; and "Dictionary of Antibacterial and Antifungus Agents", edited by Japan Bacteria and Fungi Controlling Society.
In the present invention, the pH value of the washing water is 4 to 9 and preferably 5 to 8. The temperature and time of the water washing process may vary depending on, for instance, the properties and applications of the light-sensitive materials to be processed, but in general the water washing is performed at a temperature of 15 to 45°C for 20 seconds to 10 minutes and preferably 25 to 40°C for 30 seconds to 5 minutes.
In the invention, the light-sensitive materials are directly processed with a stabilization solution instead of the water washing process. In such a stabilization process, any known methods disclosed in J.P. KOKAI Nos. 57-8543, 58-14834 and 60-220345 can be employed.
Additionally, the stabilization process may be carried out subsequent to the water washing process and examples thereof are stabilization baths containing formalin and a surfactant, which is used as the final bath for processing color light-sensitive materials for taking photographs. The stabilization solution may also contain a variety of chelating agents and/or antifungus agents.
The overflows associated with the supplementation of a replenisher to the water washing and/or stabilization processes may be introduced into other baths such as those for the desilvering process to reuse them.
The silver halide color light-sensitive materials processed by the invention may contain a developing agent for simplification of processes and rapid processing. For that purpose, it is preferable to use a variety of precursors of the color developing agents. Examples thereof include indoaniline compounds as disclosed in U.S. Patent No. 3,342,597; Schiff base type compounds as disclosed in U.S. Patent No. 3,342,599 and Research Disclosure Nos. 14850 and 15159; aldol compounds as disclosed in Research Disclosure No. 13924; metal complex salts as disclosed in U.S. Patent No. 3,719,492; and urethane type compounds as disclosed in J.P. KOKAI No. 53-135628.
For the purpose of promoting color development, the silver halide color light-sensitive materials processed by the invention may optionally comprise various 1-phenyl-3-pyrazolidones. Typical examples of such compounds are disclosed in, for instance, J.P. KOKAI Nos. 56-64339; 57-144547 and 58-115438.
In the present invention, each processing solution is used at a temperature of 10 to 50°C . It generally ranges from 33 to 38"C , but higher temperature may be used to promote the processing and to thus reduce the processing time, or a lower temperature may also be used to improve the quality of images or the stability of the processing solution. Moreover, to save the amount of silver in the color light-sensitive materials, processings utilizing cobalt intensifier or hydrogen peroxide intensifier disclosed in German Patent No. 2,226,770 and U.S. Patent No. 3,674,499 can be employed.
Each processing bath may be provided with a heater, a temperature sensor, a level sensor, a circulation pump, a filter, a floating cover, a squeezy and the like according to need.
Moreover, if a continuous processing is performed, the composition of each processing solution should be maintained by adding a replenisher for each processing solution to achieve uniform finishing of the processed materials. The amount of the replenisher can be reduced to half or less of the standard replenished amount for cutting the cost.

EXAMPLE

The present invention will hereunder be explained in more detail with reference to the following Examples, but the present invention is not restricted to these Examples.

Example 1

A multi-layered color light-sensitive material (Sample 101) was prepared by applying in order coating solutions having the following compositions on the surface of a substrate of cellulose triacetate to which an underlying layer had been applied.

(Composition of the Light-sensitive Layer)

In the following composition, the coated amounts are expressed in g/ m² of elemental silver for silver halide and colloidal silver; in g/ m² for couplers, additives and gelatin; and in moles per mole of silver halide included in the same layer for sensitizing dyes.

1st Layer: Halation Inhibiting Layer
2nd Layer: Intermediate Layer
3rd Layer: First Red-sensitive Emulsion layer
4th Layer: Second Red-sensitive Emulsion Layer
6th Layer: Intermediate Layer
7th Layer: First Green-sensitive Emulsion Layer
8th Layer: Second Green-sensitive Emulsion Layer
9th layer: Third Green-sensitive Emulsion Layer
11th Layer: First Blue-sensitive Emulsion Layer
12th Layer: Second Blue-sensitive Emulsion Layer
13th Layer: First Protective Layer
14th Layer: Second Protective Layer

To each layer there was added a surfactant as a coating aid in addition to the foregoing components.
The chemical structures or the chemical names of the compounds used in this Example are as follows:

Oil - 1 Tricresyl Phosphate
Oil- 2 Dibutyl Phthalate
Oil - 3 _Bi_s(₂-_ethylhexyl)Phthalate
H-1
- CHz =CH-S0₂- CH₂-CONH- CH₂
- I CHz =CH-SO₂-CH₂-CONH-CH₂

A multilayered color light-sensitive material (Sample 102) was prepared by applying in order coating solutions having the following compositions onto the surface of a substrate of cellulose triacetate to which an underlying layer had been applied.

(Composition of the Light-sensitive Layer)

In the following composition, the coated amounts are expressed in g/ m² , that of silver halide is expressed in the reduced amount of elemental silver. The coated amount of sensitizing dyes is expressed in moles per mole of silver halide included in the same layer.

(Sample 102)

1st Layer: Halation Inhibiting Layer
2nd Layer: Intermediate Layer
3rd Layer: First Red-sensitive Emulsion Layer
4th Layer: Second Red-sensitive Emulsion Layer
5th Layer: Third Red-sensitive Emulsion Layer
6th Layer: Intermediate Layer
7th Layer: First Green-sensitive Emulsion Layer
8th Layer: Second Green-sensitive Emulsion Layer
9th Layer: Third Green-sensitive Emulsion Layer
10th Layer: Yellow Filter Layer
11th Layer: First Blue-sensitive Emulsion Layer
12th Layer: Second Blue-sensitive Emulsion Layer
13th Layer: Third Blue-sensitive Emulsion Layer
14th Layer: First Protective Layer
15th Layer: Second Protective Layer

To each layer, there were added, in addition to the foregoing components, a gelatin hardening agent H-1 and a surfactant.

H B S - 1 Tricresyl Phosphate
H B S - 2 Dibutyl Phthalate
H B S - 3 Bis(2-ethylhexyl)Phthalate

Sensitizing Dyes
A multilayered color light-sensitive material (Sample 103) was prepared by applying in order coating solutions having the following compositions onto the surface of a substrate of cellulose triacetate film to which an underlying layer had been applied.

(Composition of the Light-sensitive Layer)

The coated amount of silver halide and colloidal silver is expressed in g/m² of elemental silver; those of couplers, additives and gelatin are expressed in g/m² and that of sensitizing dyes is expressed in moles per mole of silver halide included in the same layer.

1st Layer: Halation Inhibiting Layer
2nd Layer: Intermediate Layer
3rd Layer: Low sensitive Red-sensitive Emulsion Layer
4th Layer: High Sensitive Red-sensitive Emulsion Layer
5th Layer: Intermediate Layer
6th Layer: Low Sensitive Green-sensitive Emulsion Layer
7th Layer: High Sensitive Green-sensitive Emulsion Layer
8th Layer: Intermediate Layer
9th Layer: Donor Layer Having Interlayer Effect for Red-sensitive
10th Layer: Yellow Filter Layer
11th Layer: Low Sensitive Blue-sensitive Emulsion Layer
12th Layer: High Sensitive Blue-sensitive Emulsion Layer
13th Layer: First Protective Layer
14th Layer: Second Protective Layer

To each layer, there were added, in addition to the foregoing components, a stabililzer for the emulsion Cpd-3 in an amount of 0.04 g/ m² and a surfactant Cpd-4 as a coating aid in an amount of 0.02 g/ m².

Solv - 1 Tricresyl Phosphate
Solv - 2 Dibutyl Phthalate

H- 1
- CH₂ = CH- S0₂ - CH₂ - CONH- CH₂
- CH₂= CH- SO₂- CH₂- CONH- CH₂

Samples 104 to 106 were prepared in the same manners as those for preparing Samples 101 to 103 except that all the silver halide emulsions were replaced with silver bromide emulsions.
The color photographic light-sensitive materials (Samples 101 to 106) prepared above were exposed to light and then were processed according to the following processes utilizing an automatic developing machine till the cumulative amount of a bleach-fixing solution replenished reached three times the volume of the tank for the mother liquor thereof.
The composition of each processing solution is as follows:

(Bleaching Solution): Tank Soln. and Replenisher

(Bleach-fixing Solution): Tank Soln. and Replenisher

(Water Washing Solution): Tank Soln. and Replenisher

This was prepared by passing tap water through a mixed bed column packed with an H-type strong acidic cation-exchange resin (available from Rohm & Haas Co. Ltd. under the trade name of Amberlite IR-120B) and an OH-type anion-exchange resin (available from the same company under the trade name of Amberlite IR-400) to reduce the concentrations of calcium and magnesium ions to a level of not more than 3 mg/l , respectively and then adding 20 mg/9 of sodium dichloroisocyanurate and 1.5 g/l of sodium sulfate. The pH value of the solution was in the range of 6.5 to 7.5.

(Stabilization Solution): Tank Soln. and Replenisher

Then, a column packed with 120 ml of a strong basic anion-exchange resin (available from MITSUBISHI CHEMICAL INDUSTRIES LTD. under the trade name of DIAION PA 418) was incorporated into a piping of a pumping system for circulating the bleach-fixing solution and the light-sensitive materials were continuously processed (processing method B) after imagewise exposing to light. Further, the continuous processing was performed by changing the amount of the ion-exchange resin to be packed in the column as listed in Table I. After each continuous processing, Samples which had been exposed to light (4800° K; 100 CMS) were processed and the amount (u g/cd) of residual silver thereon was estimated by fluorescent X-rays technique. In addition, Samples which was not exposed to light (unexposed Samples) were likewise continuously processed and the amount of residual silver was examined. The results obtained are summarized in Table I below. In these tests, the amount (flow rate) of the processing solution circulated by the circulation pump was 5 l /min. Columns of a variety of sizes were used depending on the amount of the resin to be packed, for instance, a cylindrical column having a diameter of 4.6 cm and a length of a 12 cm was used for packaging 120 ml of the resin. Both ends thereof were sealed with fine mesh net of a plastic to confine the particulate resin in the column.
As seen from Table I, the residual amount of silver becomes low (exposed Samples) if the light-sensitive materials continuously processed contain silver iodide, in the processing method wherein the bleach-fixing solution is treated with an ion-exchange resin. It is thought that this is due to the enhancement in the fixing ability of the solution since there is almost no difference between the amounts of residual silver of the exposed and unexposed Samples.

Example 2

Preparation of-Tabular Silver Iodobromide Grains

Gelatin (30 g) and potassium bromide (6 g) were added to one liter of water contained in a container and an aqueous solution of silver nitrate (containing 5 g of silver nitrate) and a solution of 0.15 g of potassium iodide in water were added to the container maintained at 60°C over one minute with stirring by a double jet technique. Moverover, an aqueous solution containing 145 g of silver nitrate and an aqueous solution containing 4.2 g of potassium iodide were also added to the container by a double jet technique. In this respect, the rate of addition of the solutions was accelerated so that the rate at the end of the addition is 5 times that at the initiation of the addition. After the addition was completed, soluble salts were removed at 35°C by settling followed by raising the temperature to 40^*C , additionally adding 75 g of gelatin and adjusting pH to 6.7. Thus, there was obtained an emulsion containing tabular silver iodobromide grains whose diameter of the projected area was 0.98 µ , whose average thickness was.0.138 µ and whose silver iodide content was 3 mole%. This emulsion was chemically sensitized by the combination of gold and ion sensitization.
A surface protective layer was ontained utilizing a gelatin solution containing polyacrylamide having an average molecular weight of 8,000, sodium polystyrene sulfonate, fine particles of polymethyl methacrylate (average particle size = 3.0µ ), polyethylene oxide and a film hardening agent in addition to gelatin. Further, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 2,6-bis(hydroxylamino)-4-diethylamino-1. 3,5-triazine and nitron as stabilizers; trimethylolpropane as an antidrying and antifoggant; a coating aid, and a film hardening agent were added to obtain a coating solution. Then, the coating solution was applied to both sides of a polyethylene terephthalate substrate simultaneously with surface protective layers and was dried to form a photographic material (Sample 201). The coated amount of silver of each photographic material is listed in the following Table.

Processing I

The processing I will be detailed below. (Formulation of Developer): for obtaining 38 liters thereof.

Part A
Part B
Part C
Starter

(Method for Preparing the Developing Solution)

20 Liters of water was introduced into a tank for storing a replenisher having a volume of about 50 liters, the aforementioned Part A, Part B and Part C were in order added thereto with stirring to dissolve these and then water was added thereto to obtain a solution of 38 liters which was used as the replenisher for developer (pH 10.30).
A tank for development of an automatic developing machine was first filled with a developer obtained by mixing the replenisher for developer with the foregoing starter in a rate of 20 ml of the latter per liter of the former (pH 10.15). Thereafter, the replenisher for developer was supplemented in a rate of 45 ml per sheet of quart (10 inch x 12 inch) as the light-sensitive materials were processed.

(Formulation of Fixing Solution): for 38 liters.

Part A

Part B

(Method for Preparing Fixing Solution)

20 Liters of water was introduced into a tank for storing a replenisher having a volume of about 50 liters, then the foregoing Part A and Part B were in order added thereto to dissolve these with stirring and water was added to form 38 liters of a fixing solution.
A tank for fixing treatment of an automatic developing machine was first filled with the replenisher for fixing solution as such (pH 4.25). Thereafter, the replenisher for fixing processing was supplemented to the tank in an amount of 30 ml per sheet of quart (10 inch x 12 inch) as the light-sensitive materials were processed.
Then, the light-sensitive materials were continuously processed utilizing a variety of anion-exchange resins which were incorporated into a piping system of a pump for circulating the fixing solution as in Example 1 till the cumulative amount of replenisher supplemented reached three times the volume of the tank for fixing treatment, thereafter the unexposed light-sensitive material (Sample 201) was processed and then the amount of residual silver was estimated. The results observed are listed in Table II below.
As seen from the results listed in Table II, preferred results in which the amount of the residual silver is very small are obtained by using strong basic anion-exchange resins as compared with those observed when the weak basic anion-exchange resin is utilized.

Example 3

Sample 101 obtained in Example 1 was imagewise exposed to light and then continuously processed in accordance with the following process A.
Each processing solution used has the following composition.

(Bleach-fixing Solution)

(Water Washing Solution): Tank Soln. and Replenisher

This was prepared by passing tap water through a mixed bed column packed with an H-type strong acidic cation-exchange resin (available from Rohm & Haas Co., Ltd. under the trade name of Amberlite IR-120B) and an OH-type anion-exchange resin (available from the same company under the trade name of Amberlite IR-400) to reduce concentrations of magnesium and calcium ions to not more than 3 mg/l respectively and then adding 20 mg/l of sodium dichloroisocyanurate and 0.15 g/l of sodium sulfate.
The pH value of this solution ranges from 6.5 to 7.5.
As in Example 1, 120 ml each of various resins was filled in a column and installed in a system for circulating a bleach-fixing solution (processings B, C, D, E, F, G and H).
6,000 m of Sample 101 was continuously processed in each processing A to H (1000l of the bleach-fixing solution per liter of the resin). Then, Sample 101 was exposed to light (100 CMS), processed according to each processing and the amount of residual silver was determined by fluorescent-X rays technique. The results obtained are summarized in Table III (exposed Sample).
It is found that the desilvering properties of the present invention is enhanced due to the improvement in fixing ability, since there is almost no difference between the residual amount of silver of the exposed and unexposed Samples. In particular, marked effects were obtained by the processings D to H.

(Example 4)

Sample 101 obtained in Example 1 was imagewise exposed to light and then continuously processed by the following processing I.
Processing solutions used are as follows:

(Bleaching Solution)

(Fixing Solution)

As in Example 3, ion-exchange resins were used (processings J, K. L and M). Sample 102 was exposed to light through a continuous tone wedge (at 10 CMS) and the foregoing Sample was processed at the beginning and the end of the continuous processing to determine the amount of residual silver on the maximum density region and the minimum density (Dc min) of magenta (exposed Sample). Then, unexposed Sample was likewise processed to determine the amount of residual silver. The results obtained are summarized in Table IV.
The present invention does not cause incomplete desilvering due to insufficient fixing and any increase in magenta stain (Dc min) and provides processed material having good photographic properties.

Claims

1. A method for processing silver halide photographic light-sensitive materials which comprises developing a silver halide photographic light-sensitive material composed of a substrate provided thereon with at least one light-sensitive silver halide emulsion layer containing silver iodide and then processing the material with a processing solution having fixing ability, characterized in that the processing with the processing solution having fixing ability is performed while a part or whole of the processing solution having fixing ability is brought into contact with an anion-exchange resin and that 20 to 2,000 of the processing solution having fixing ability per liter of the anion-exchange resin is brought into contact with the resin.

2. The method of claim 1 wherein the processing with the processing solution having fixing ability is performed using a processing solution having fixing ability which contains the anion-exchange resin.

3. The method of claim 1 wherein a part or whole of the used processing solution having fixing ability is brought into contact with the anion-exchange resin and it is used in the processing with the processing solution having fixing ability.

4. The method of claim 1 wherein the content of silver iodide in the silver halide emulsion layer is not less than 1 mole%.

5. The method of claim 4 wherein the content of silver iodide in the silver halide emulsion layer ranges from 5 to 25 mole%.

6. The method of claim 1 wherein the anion-exchange resin is a basic anion-exchange resin.

7. The method of claim 6 wherein the basic anion-exchange resin is a strong basic anion-exchange resin.

8. The method of claim 1 wherein the processing with the processing solution having fixing ability is a bleach-fixing processing.

9. The method of claim 1 wherein the coated amount of silver of the light-sensitive material ranges from 2 to 10 g/m² .

10. The method of claim 6 wherein the basic anion-exchange resin is a resin represented by the following general formula (VIII):

[wherein A represents a monomer unit obtained by copolymerizing copolymerizable monomers having at least two copolymerizable ethylenically unsaturated groups at least one of which is included in the side chain; B represents a monomer unit obtained by copolymerizing copolymerizable ethylenically unsaturated monomers; R,₃ represents a hydrogen atom or a lower alkyl or aralkyl group; Q represents a single bond or an alkylene, phenylene or aralkylene group or a group -CO-0-L-, -CO-NH-L- or -CO-NR-L- (wherein L is an alkylene, arylene or aralkylene group and R is an alkyl group); G represents

(wherein R₁₄ to R₂₁ may be the same or different or may be substituted and each represents a hydrogen atom or an alkyl, aryl or aralkyl group and X⊖ epresents an anion), at least two groups selected from Q. R₁₄, R₁₃ and R₁₆ , or Q, R₁₇, R₁₈ , R₁₉, R₂₀ and R₂₁ may be bonded to form a ring structure together with the nitrogen atom, and x, y and z represent molar percentages, x ranges from 0 to 60, y from 0 to 60 and z from 30 to 100.]

11. The method of claim 10 wherein the basic anion-exchange resin is a resin represented by the following general formula (IX):

(wherein A, B, x, y, z, R₁₃ to R₁₆ and X⊖ are the same as those defined above in connection with the general formula (VIII)).

12. The method of claim 10 wherein G in the general formula (VIII) is

13. The method of claim 12 wherein the total number of carbon atoms of R₁₄ , R₁₅ and R₁6 is not less than 12.